AN ARTICLE HAVING A CHIP-RESISTANT ELECTRODEPOSITED COATING AND A PROCESS FOR FORMING AN ELECTRODEPOSITED COATING

Description

BACKGROUND

[0001] The present invention is directed to an article, such as an automobile body, that is electrocoated with a chip-resistant coating and a process for electrodepositing a chip-resistant coating on a substrate.

[0002] Multi-layered coating composites find use in various industries including the coating and/or painting of motor vehicles. In several of these industries, and in the automotive industry in particular, a substrate can have from two to six or more coating layers. These coating layers protect the substrate and provide a decorative finish.

[0003] Multi-layered coating composites for metal substrates often use electrodeposition coatings as an initial resinous coating layer to protect the metal substrate from corrosion. Cationic electrodeposition coatings have become the coatings of choice for corrosion protection. Electrodeposition has become increasingly important in the coatings industry because, by comparison with non-electrophoretic coating means, electrodeposition offers higher paint utilization, outstanding corrosion protection, low environmental contamination, and a highly automated process.

[0004] A spray-applied chip resistant coating layer is often present in multi-layered coating composites for motor vehicles. The chip resistant layer protects the surface of the substrates from losing paint through chipping when the vehicle is hit with solid debris, such as gravel and stones. The art for achieving chip resistance from spray applied primer coatings has postulated that reducing the differential in impact energy between the multiple coating layers should improve chip resistance of the coating. This is especially applicable when coating layers have excessive difference of hardness between them. This reduction in the differential would lessen delamination between the coatings, such as between an undercoat and an intermediate coat or between a top coat and an intermediate coat.

SUMMARY OF THE INVENTION

[0005] An object of the present invention is to provide a coating system having both good chip resistance and corrosion protection, while additionally providing efficiencies in application and processing through the elimination of a paint layer. These efficiencies include superior paint utilization, lower environmental contamination, and a highly automated process.

[0006] The present invention includes a coated article that comprises a corrosion-resistant electrically conductive substrate that is free of an electrodeposited coating and an electrodeposited film-forming composition applied to at least a portion of the surface of the corrosion-resistant electrically conductive substrate. The film forming composition includes a curable electrodepositable elastomeric polymer. The substrate typically is one of aluminum or alloys thereof, zinc or zinc alloy surface treated steel, such as galvanized steel, that is coated with a non-insulating layer of a zinc-rich or iron phosphide-rich organic coating.

[0007] The present invention also includes a process for electrocoating a corrosion-resistant electrically conductive substrate which is free of an electrodeposited coating, including the step of electrodepositing a coating composition onto a surface of the electrically conductive substrate, the coating composition including a curable elastomeric polymer.

[0008] The corrosion-resistant substrate combined with an elastomeric electrodeposited coating performs as well or better than a less corrosion-resistant substrate coated with an electrodeposited corrosion-resistant primer followed by a spray-applied primer-surface layer. The above-described coating aids in 1) bonding the finished layer(s) to the substrate, 2) preventing chipping damage, 3) leveling defects in the substrate and providing a uniform under-layer, 4) protecting repairs and cut edges, and 5) resisting damage due to exposure to ultraviolet light.

DETAILED DESCRIPTION OF THE INVENTION

[0009] The use of numerical values in the various ranges specified in this application, unless expressly indicated otherwise, are stated as approximations as though the minimum and maximum values within the stated ranges were both preceded by the word "about." In this manner slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Also, the disclosure of these ranges is intended as a continuous range including every value between the minimum and maximum values.

[0010] The present invention is directed to a coated article, typically an automobile body that includes a corrosion-resistant, electrically conductive substrate that has been coated with one or more layers of a film-forming composition. The corrosion-resistant substrate can be inherently corrosion-resistant, such as aluminum, or a substrate, such as a ferrous substrate, that has been rendered corrosion-resistant by application of a suitable pretreatment composition. The film-forming layer(s) include a layer that contains a curable, film-forming elastomeric polymer that is electrodeposited onto the corrosion-resistant, electrically conductive substrate. The elastomeric polymer preferably is a curable polyurethane, polyurea or poly(urethane-urea) that typically is the reaction product of a polyisocyanate and an active hydrogen-containing polymeric material. The active hydrogen-containing polymeric material is selected from a polyether polyamine, and/or a mixture of a polyether polyamine and a polyesterpolyol and/or a polyether polyol. The elastomeric polymer preferably contains a minimum amount of polyurea linkages when cured.

[0011] Corrosion-resistant conductive substrates include, without limitation, metal substrates such as stainless steel; zinc or zinc alloy surface treated steel, that is coated with a zinc-rich or iron phosphide-rich organic coating; aluminum; copper; magnesium or alloys thereof. By "surface treated" it is understood that the surface of the steel has a zinc or zinc alloy layer that is introduced by a variety of known processes such as by galvanizing or cladding the steel substrate. The substrate can be treated with a phosphating solution such as a zinc phosphating solution as described in US 5,588,989. Combinations or composites of ferrous and/or non-ferrous metals also can be used, such as GALVALUME, GALVANNEAL and GALFAN zinc-aluminum alloys.

[0012] The terms "corrosion-resistant," refer to the relative resistance of the substrate to corrosion as compared to cold rolled steel. By "non insulating" it is meant that a coating does not interfere in any substantial way with the electrodeposition of the film-forming composition of the present invention (i.e., render the electrodeposited layer commercially unacceptable).

[0013] The pre-treatment composition also may be a solution that comprises one or more Group IIIB or IVB element-containing compounds or mixtures thereof solubulized or dispersed in a carrier medium, typically an aqueous medium. The Group IIIB and IVB elements are defined by the CAS Periodic Table of the Elements as shown, for example, in the Handbook of Chemistry and Physics, (60th Ed. 1980). Transition metal compounds and rare earth metal compounds typically are compounds of zirconium, titanium, hafnium, yttrium and cerium and mixtures thereof. Typical zirconium compounds may be selected from hexafluorozirconic acid, alkali metal and ammonium salts thereof, ammonium zirconium carbonate, zirconyl nitrate, zirconium carboxylates and zirconium hydroxy carboxylates such as hydrofluorozirconic acid, zirconium acetate, zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, ammonium zirconium citrate, and mixtures thereof. Hexafluorozirconic acid is preferred. An example of a yttrium compound is yttrium nitrate. An example of a titanium compound is fluorotitanic acid and its salts. An example of a hafnium compound is hafnium nitrate. An example of a cerium compound is cerous nitrate. Preferably, the Group IIIB or IVB metal compounds are in the form of metal salts or acids which are water soluble. The Group IIIB or IVB metal compound is typically present in the carrier medium in an amount of 10 to 5000 ppm metal, preferably 100 to 300 ppm metal.

[0014] The pretreatment composition carrier also may contain a film-forming resin. Suitable resins include reaction products of one or more alkanolamines and an epoxy-functional material containing at least two epoxy groups, such as those disclosed in U.S. 5,653,823. Preferably, such resins contain beta-hydroxy ester, imide, or sulfide functionality, incorporated by using dimethylolpropionic acid, phthalimide, or mercaptoglycerine as an additional reactant in the preparation of the resin. Alternatively, the reaction product is that of the diglycidyl ether of Bisphenol A (commercially available from Shell Chemical Company as EPON 880), dimethylol propionic acid, and diethanolamine in a (0.6 to 5.0):(0.05 to 5.5:1) mole ratio. Other suitable resins include water soluble and water dispersible polyacrylic acids such as those as disclosed in U. S. Patents 3,912,548 and 5,328,525; phenol-formaldehyde resins as described in U. S. Patent 5,662,746 water soluble polyamides such as those disclosed in WO 95/33869; copolymers of maleic or acrylic acid with allyl ether as described in Canadian patent application 2,087,352; and water soluble and dispersible resins including epoxy resins, aminoplasts, phenol-formaldehyde resins, tannins, and polyvinyl phenols as discussed in U. S. Patent 5,449,415.

[0015] In one embodiment, the pretreatment composition includes a film-forming resin that is present in an amount of 0.005% to 30% based on the total weight of the pretreatment composition, and the above-described Group IIIB or IVB metal compound in an amount of 10 to 5000, preferably 100 to 1000, ppm metal based on total weight of the pretreatment composition. The weight ratio of the resin to Group IIIB or IVB metal or metal compound is from 2.0 to 10.0, preferably 3.0 to 5.0, based on the Group IIIB or IVB metal.

[0016] Non-ferrous or ferrous substrates can be pretreated with a non-insulating layer of organophosphates or organophosphonates such as those described in U.S. Patents No 5,294,265 and 5,306,526. Such organophosphate or organophosphonate pretreatments are available commercially from PPG Industries, Inc. under the trade name NUPAL®. Application to the substrate of a non-conductive coating, such as NUPAL, typically is followed by the step of rinsing the substrate with deionized water prior to the coalescing of the coating. This ensures that the layer of the non-conductive coating is sufficiently thin to be non-insulating.

[0017] The pretreatment coating composition can further comprise surfactants that function as aids to improve wetting of the substrate. Generally, the surfactant materials are present in an amount of less than about 2 weight percent on a basis of total weight of the pretreatment coating composition. Other optional materials in the carrier medium include defoamers and substrate wetting agents.

[0018] Preferably, the pretreatment coating composition is essentially free of chromium-containing materials, i.e., the composition contains less than about 2 weight percent of chromium-containing materials (expressed as CrO₃), and more preferably less than about 0.05 weight percent of chromium-containing materials. Examples of such chromium-containing materials include chromic acid, chromium trioxide, chromic acid anhydride, dichromate salts such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium, barium, magnesium, zinc, cadmium and strontium dichromate. Most preferably, the pretreatment coating composition is free of chromium-containing materials.

[0019] In a typical pre-treatment process, before depositing the pre-treatment composition upon the surface of the metal substrate, it is preferred to remove foreign matter from the metal surface by thoroughly cleaning and degreasing the surface. The surface of the metal substrate can be cleaned by physical or chemical means, such as by mechanically abrading the surface or cleaning/degreasing with commercially available alkaline or acidic cleaning agents which are well know to those skilled in the art, such as sodium metasilicate and sodium hydroxide. Example of a preferred cleaning agent is CHEMKLEEN® 163, an alkaline-based cleaner commercially available from PPG Pretreatment and Specialty Products of Troy, Michigan. Following the cleaning step, the metal substrate is usually rinsed with water in order to remove any residue. The metal substrate can be air-dried using an air knife, by flashing off the water by brief exposure of the substrate to a high temperature or by passing the substrate between squeegee rolls. The pretreatment coating composition can be deposited upon at least a portion of the outer surface of the metal substrate. Preferably, the entire outer surface of the metal substrate is treated with the pretreatment composition. The thickness of the pretreatment film can vary, but is generally less than about 1 micrometer, preferably ranges from 1 to 500 nanometers, and more preferably ranges from 10 to 300 nanometers.

[0020] When the substrate comprises an aluminum alloy it is particularly important to avoid over-cleaning the substrate with cleaning agents such as CHEMKLEEN® 163.

[0021] It is postulated, without any intention of being bound by this theory, that the over-cleaning of the substrate with these agents damages the surface of the substrate, resulting in the exposure of and/or the release of Fe and Cu, which adversely affects the quality of the chip-resistant layer. A typical non-damaging time range for the exposure of the substrate to these cleaning agents is from one to two minutes. Damage to the surface of the substrate can be monitored empirically by taking gloss readings of the subsequent baked electrocoated layer. For example, it has been determined that typical aluminum alloys should not be treated for more than two minutes with the commercially available CHEMKLEEN® CK166HP/CKl71 product (PPG Pretreatment and Specialty Products of Troy Michigan).

[0022] The pretreatment coating composition is applied to the surface of the metal substrate by any conventional application technique, such as by spraying, immersion or roll coating in a batch or continuous process. The temperature of the pretreatment coating composition at application is typically 10°C to 85°C, and preferably 15°C to 60°C. The pH of the preferred pretreatment coating composition at application generally ranges from 2.0 to 5.5, and is preferably 3.5 to 5.5. The pH of the medium may be adjusted using mineral acids such as hydrofluoric acid, fluoroboric acid and phosphoric acid including mixtures thereof; organic acids such as lactic acid, acetic acid, citric acid, sulfamic acid, or mixtures thereof; and water soluble or water dispersible bases such as sodium hydroxide, ammonium hydroxide, ammonia, or amines such as triethylamine, methylethyl amine, or mixtures thereof.

[0023] Continuous processes typically are used in the coil coating industry and also for mill application. The pretreatment coating composition can be applied by any of these conventional processes. For example, in the coil industry, the substrate typically is cleaned and rinsed and then contacted with the pretreatment coating composition by roll coating with a chemical coater. The treated strip is then dried by heating, painted and baked by conventional coil coating processes.

[0024] Mill application of the pretreatment composition can be by immersion, spray or roll coating applied to the freshly manufactured metal strip. Excess pretreatment composition is typically removed by wringer rolls. After the pretreatment composition has been applied to the metal surface, the metal can be rinsed with deionized water and dried at room temperature or at elevated temperatures to remove excess moisture from the treated substrate surface and cure any curable coating components to form the pretreatment coating. Alternately, the treated substrate can be heated at 65°C to 125°C for 2 to 30 seconds to produce a coated substrate having a dried residue of the pretreatment coating composition thereon. If the substrate is already heated from the hot melt production process, no post application heating of the treated substrate is required to facilitate drying. The temperature and time for drying the coating will depend upon such variables as the percentage of solids in the coating, components of the coating composition and type of substrate.

[0025] The film coverage of the residue of the pretreatment composition generally ranges from 1 to 10,000 milligrams per square meter (mg/m²), and is preferably 10 to 400 mg/m².

[0026] A layer of a weldable primer also may be applied to the substrate, whether or not the substrate is pretreated. Preferably the substrate is pretreated. A typical weldable primer is BONAZINC®, a zinc-rich mill applied organic film-forming composition, which is commercially available from PPG Industries, Inc., Pittsburgh, Pennsylvania. BONAZINC® typically is applied to a thickness of at least/micrometer and preferably to a thickness of about 3-4 micrometers. Other weldable primers, such as iron phosphide-rich primers, are commercially available.

[0027] The chip-resistant film coating of the present invention is then applied to the corrosion-resistant electrically conductive substrate. The coating is electrodeposited from a composition that includes an ionic, elastomeric polymer, typically a polyurea, a polyurethane or a poly(urethane-urea). The elastomeric polymer typically is the reaction product of a polyisocyanate and an active hydrogen-containing polymer that is one of a polyester, a polyether, an acrylic polymer or combinations thereof. The elastomeric polymer is the reaction product of a polyisocyanate and an active hydrogen-containing polymer selected from a polyether polyamine, and/or a mixture of a polyether polyamine and a polyester polyol and/or a polyether polyol. A suitable active hydrogen-containing polymer has a Tg of less than 0°C and a number average molecular weight of 400-4000. Examples of suitable active hydrogen-containing polymer (polyols) are described in U.S. Patent No. 4,154,891. The Tg for many polymers, including polyethers are available in the literature and/or are determinable by well-known methods, such as by differential scanning calorimetry. Also helpful in determining the Tg is the Clash-Berg method (ASTM D-1043, a method for determination of the stiffness characteristics of plastics over a wide temperature range by direct measurement of the apparent modulus of rigidity). The elastomeric polymer typically has a flexibilizing segment content of from 30 to 100, preferably from 40 to 60. The flexibilizing segment content is determined in accordance with Example 1 part D.

[0028] The elastomeric polymer is ionic to permit electrodeposition of a resin formed therefrom. The ionic resin can be anionic or cationic, but preferably is cationic, the composition including the ionic resin being cationically electrodepositable. The elastomeric polymer typically has a weighted average molecular weight (Mw) of less than 100,000, preferably less than 50,000 and most preferably from 10,000 to 40,000. The elastomeric polymer also typically has active hydrogen functionality, i.e., hydroxyl, primary or secondary amine, and typically has an active hydrogen equivalent weight of 800 to 2,500 grams per equivalent. The molecular weight of the elastomeric polymer and other polymeric materials used in the practice of the invention is determined by gel permeation chromatography using a polystyrene standard. The elastomeric polymer preferably is essentially aliphatic to render the polyurethane or polyurea less susceptible to damage by UV radiation. By "essentially aliphatic" it is meant that the backbone of the elastomeric polymer contains no more than 50% by weight aromatic groups or moieties (i.e., the total weight of multivalent phenyl groups, such as phenylene ((M_w=76), in the backbone)), preferably no more than 20% by weight aromatic groups, most preferably no more than 5% by weight aromatic groups and optimally <1% by weight aromatic groups. The percentage by weight of aromatic groups (A%) can be determined by the following formula:

where W_a is the weight of aromatic groups in the aromatic group-containing reactant, which is the weight of the aromatic group-containing reactant multiplied by the fraction of the total weight of the aromatic group-containing reactant that is aromatic, which can be calculated as follows:

W_t is the total weight of the reactants less the total weight of materials lost to volatilization during the synthesis and cure of the polymer. If more than one reactant contains aromatic groups, A% for each reactant can be added (i.e., A%₁ + A%₂ = A%_total).

[0029] The elastomeric polymer typically is a polyurethane, a polyurea or a poly(urethane-urea). The elastomeric polymer preferably includes a minimum amount of urea linkages in its cured state. Typically, the minimum amount of urea linkages are greater than about 0.50 meq/g of cured film, preferably greater than about 0.60 meq/g of cured film and most preferably greater than about 1.00 meq/g of cured film. The meq/gram can be determined by determining the total meqs of urea linkages formed divided by the total weight in grams of the reactants used in preparing the polymer minus the weight of molecules lost, for example, by volatilization, in curing the film. For example, a polymer prepared from reactants containing 2 equivalents of isocyanate, 1 equivalent of amine and 1 equivalent of hydroxyl groups in 1000 grams of reactants would contain 1 equivalent of urea linkages and 1 equivalent of urethane linkages per 100 grams of cured film (assuming no loss of volatile molecules), which is the equivalent of 1 meq of urea linkages per gram of cured film. In practice, it is found that films that contain a minimum percent of urea linkages are more stable under typical baking (curing) temperatures, as compared to urethane linkages, which are less tolerant of overbalong.

[0030] Polyurethanes and polyureas typically are produced by reacting a polyisocyanate and an active hydrogen-containing polymer. Suitable polyisocyanates useful for preparing the elastomeric polymer include those that have aliphatically-, cycloaliphatically-, araliphatically- and/or aromatically-bound isocyanate groups. Preferably, the polyisocyanate is aliphatic or cycloaliphatic.

[0031] Examples of aliphatic and cycloaliphatic polyisocyanates include 4,4-methylenebisdicyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI)(i.e., 1,6-hexamethylene diisocyanate), isophorone diisocyanate (IPDI), methylenebis(cyclohexyl isocyanate), cyclohexylene diisocyanate (hydrogenated XDI) and isocyanurates thereof.

[0032] Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI) (i.e., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or a mixture thereof), diphenylmethane-4,4-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3-dimethyl-4,4-biphenylene diisocyanate (TODI), crude TDI (i.e., a mixture of TDI and an oligomer thereof), polymethylenepolyphenyl polyisocyanate, crude MDI (i.e., a mixture of MDI and an oligomer thereof), xylylene diisocyanate (XDI) and phenylene diisocyanate.

[0033] Polyisocyanate derivatives prepared from hexamethylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, including isocyanurates thereof, and/or 4,4'-bis(isocyanatocyclohexyl)methane are suitable.

[0034] The amount of polyisocyanate used to make the elastomeric polymer is typically from 10 to 60, preferably 20 to 50 percent by weight based on total weight of the reactants used to make the elastomeric polymer.

[0035] The active hydrogen-containing material for reaction with the polyisocyanate to form the cationic or anionic polyurethane comprises one or more active hydrogen-containing polymers. These materials preferably have an average active hydrogen functionality ranging from 2 to 8, preferably from 2 to 4, a number average molecular weight ranging preferably from 400 to 10,000, more preferably from 400 to 4,000, and a glass transition temperature (Tg) of 0°C or less. Polyether polyols or polyamines are preferred. Polyether polyamines are most preferred.

[0036] The term "active hydrogen" means those groups which are reactive with isocyanates as determined by the Zerewitnoff test as is described in the Journal Of The American Chemical Society, Vol. 49, page 3181 (1927). Preferably, the active hydrogens are hydroxyl, primary amine and secondary amine. Most preferably, the active hydrogens are amines.

[0037] Examples of polyether polyols are polyalkylene ether polyols that include those having the following structural formula:

where the substituent R is hydrogen or lower alkyl containing from 1 to 5 carbon atoms including mixed substituents, and n is typically from 5 to 200. Included are, without limitation, poly(oxytetramethylene) glycols, poly(oxyethylene) glycols, poly(oxy-1,2-propylene) glycols and the reaction products of ethylene glycol with a mixture of 1,2-propylene oxide and ethylene oxide. These materials are obtained by the polymerization of alkylene oxides such as ethylene oxide, propylene oxide and tetrahydrofuran.

[0038] Also, polyethers obtained from the oxyalkylation of various polyols, for example, diols such as 1,6-hexanediol or higher polyols such as trimethylolpropane and sorbitol, can be used. One commonly utilized oxyalkylation method is the reacting of a polyol with alkylene oxide such as ethylene or propylene oxide in the presence of an acidic or basic catalyst.

[0039] Examples of polyamines are polyoxyalkylene polyamines. The preferred polyamines are polyoxyalkylene polyamines of the structure:

wherein R can be the same or different and is selected from the class consisting of hydrogen, lower alkyl radicals having from 1 to 6 carbon atoms, and n represents an integer of from about 1 to 50, preferably 1 to 35. A number of such polyoxyalkylene polyamines are described in more detail in U.S. Pat. No. 3,236,895, column 2, lines 40-72; methods of preparation of the polyoxyalkylene polyamines are illustrated in the patent in Examples 4, 5, 6 and 8-12 in columns 4 to 9 thereof; the aforementioned portions of U.S. Pat. No. 3,236,895.

[0040] Mixed polyoxyalkylene polyamines can be used, that is, those in which the oxyalkylene group can be selected from more than one moiety. Examples are polyoxyethylene-propylene polyamines such as those having the following structural formula:

wherein n+m is equal to 1 to 50, preferably 1 to 35, m is equal to 1 to 49, preferably 1 to 34, and n is equal to 1 to 34.

[0041] Besides the polyoxyalkylene polyamines mentioned above, derivatives of polyoxyalkylene polyamines or polyols also may be usable. Examples of suitable derivatives are aminoalkylene derivatives which are prepared by reacting polyoxyalkylene polyamines or polyols such as those mentioned above with acrylonitrile followed by hydrogenation of the reaction product. An example of a suitable derivative is that of the following structural formula:

wherein X is O or NH, Y is a C_1-6 alkylene group and n is 1-50.

[0042] In one particular embodiment, the polyoxyalkylene polyamine is polyoxytetramethylene diamine, which typically is the hydrogenation product of cyanoethylated polyoxytetramethylene diol (obtained from polyoxytetramethylene diol and acrylonitrile).

[0043] Therefore, in the practice of the invention, where the expression "polyoxyalkylene polyamines" is used, what is intended are polyamines containing both oxyalkylene groups and at least two amine groups, preferably primary amine groups, per molecule. Primary amines are considered to be monofunctional when reacting with isocyanate groups to form a urea linkage.

[0044] Preferred active hydrogen-containing polyethers are polyoxytetramethylene diols or diamines, such as polytetrahydrofuran and polyoxypropylene diamine or mixed polyoxyethylene-propylene diamines. Polyoxypropylene diamine and polyoxytetramethylene diamine are most preferred.

[0045] The polyether segment can be derived from a single polyether polyol or polyamine or various blends thereof. Preferred are blends of polyether polyols such as polyoxytetramethylene diol and polyether polyamines such as polyoxypropylene diamine polyoxytetramethylene diamine or in weight ratios of 0.5-10:1, preferably 1 to 7:1.

[0046] Besides active hydrogen-containing polyethers, other active hydrogen-containing materials can be reacted with the polyisocyanate to provide the elastomeric segment. To produce polyurethanes, examples include polycarbonate diols, polyester diols, hydroxyl-containing polydiene polymers, hydroxyl-containing acrylic polymers, and mixtures thereof. To produce polyureas, examples include without limitation, polycarbonated amines, polydienediamines and iminated polyester.

[0047] Examples of polyester polyols and hydroxyl-containing acrylic polymers are described in U.S. Patent Nos. 3,962,522 and 4,034,017, respectively. Examples of polycarbonate polyols are described in U.S. Patent No. 4,692,383 in col. 1, line 58 to col. 4, line 14. Examples of hydroxyl-containing polydiene polymers are disclosed in U.S. Patent No. 5,863,646, col. 2, lines 11-54. These polymeric polyols will have number average molecular weights of from 400 to 10,000, preferably from 400 to 3,000.

[0048] The amount of the active hydrogen-containing polymer that is used to prepare the elastomeric polymer is at least 30 percent by weight, preferably at least 35 percent by weight, and more preferably from 35 to 50 percent by weight based on total weight of the reactants used to make the elastomeric polymer.

[0049] Low molecular weight active hydrogen-containing materials, such as polyols or polyamines having two to four hydroxyl or amine groups and molecular weights of less than 400, preferably less than 250 and most preferably between 62 and 250, also can be included as reactants for preparing the polyurethane. Specific examples include alkylene diols having 1 to 10 carbon atoms such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, ethylene diamine, hexamethylene diamine, trimethylolpropane, glycerol, pentaerythritol and sorbitol. Examples of other low molecular weight polyols are ether polyols such as diethylene glycol and ethoxylated Bisphenol A.

[0050] The low molecular weight polyols or polyamines are used in amounts up to 30 percent by weight, preferably from 0.5 to 10 percent by weight based on weight of the reactants used to make the elastomeric polymer.

[0051] The elastomeric polymer formed from the reaction of the polyisocyanate and the active hydrogen-containing material typically contains ionizable groups, which can be ionized to solubilize the polymer in water, or groups can be reacted with an ionizable material to form an ionizable group. For the purposes of this invention, the term "ionizable" means a group capable of becoming ionic, i.e., capable of dissociating into ions or becoming electrically charged. The ionizable moiety can be provided as a group present on the active hydrogen-containing material or as part of a second active hydrogen-containing material that is co-reacted with, or attached to, the active hydrogen-containing compound and the polyisocyanate. A preferred embodiment is a cationic polyurea that is substantially free of polyurethane linkages.

[0052] For the cationic polymers, the ionizable moiety typically is a tertiary amine group that can be incorporated into the polymer by reaction of the polymer with a co-reactive material containing the ionizable moiety (the tertiary amine group). The amine is neutralized with acid to form an amine salt group. Such compounds include aminoalcohols such as dimethylaminoethanol, dimethylaminopropanol, aminopropyldiethanolamine, diethylaminopropylamine, hydroxyalkylmorpholine like hydroxyethylmorpholine, and hydroxyalkylpiperazine like hydroxyethylpiperazine and mixtures thereof. The amount of amine introduced into the polymer typically is that sufficient to give 0.1 to 1, preferably 0.2 to 0.5 milliequivalents (meqs) of amine per gram of resin solids as determined by titration.

[0053] In a further embodiment, the elastomeric polymer can be prepared to include pendant epoxy groups, i.e., by the use of glycidol as an active hydrogen-containing compound, which can be reacted with a tertiary amine in the presence of an organic acid to form a quaternary amonium group or with a sulfide, such as thiodiethanol, in the presence of an organic acid to form a sulfonium group. A method for forming quaternary amonium groups is described in U.S. Patent No. 5,908,912. A method for forming sulfonium groups is described in U.S. Patents No. 3,793,278 and 3,959,106.

[0054] For the anionic polymer, the ionizable moiety is an acid group which typically is incorporated into the polymer by reaction with an active hydrogen-containing compound. The acid is neutralized with base to form the anionic salt group. Examples of anionic groups are -OSO₃^- , -COO^-, -OPO₃⁼, -SO₂O^-, -POO^-; and PO₃⁼, with COO^- being preferred.

[0055] Suitable materials for introducing acid groups into the anionic polymer are hydroxy and mercapto carboxylic acids. Specific examples include dimethylolpropionic acid, which is preferred, glycolic acid and lactic acid. Other examples of compounds which contain active hydrogens and acid groups are amino carboxylic acids, amino hydroxy carboxylic acids, sulfonic acids, hydroxy sulfonic acids and amino sulfonic acids. Examples include oxaluric acid, anilido acetic acid, glycine, 6-amino-caprylic acid, reaction product of ethanolamine and acrylic acid, hydroxyethylpropionic acid, 2-hydroxy-ethane sulfonic acid and sulphanilic acid. Amino acids must be used in the presence of base such as potassium hydroxide or a tertiary amine. The amount of acid incorporated into the polymer typically is that sufficient to give the polymer 0.1 to 1, preferably 0.2 to 0.5 meqs of acid per gram of resin solids as determined by titration.

[0056] The amine or the acid groups are neutralized with acid and base, respectively. Neutralization can range from 0.1 to 1.0, preferably 0.4 to 0.8, of the total theoretical neutralization equivalent.

[0057] For the cationic polymers, suitable neutralizing agents are organic acids such as acetic acid, boric acid, hydroxyacetic acid, propionic acid, lactic acid, formic acid, tartaric acid, sulfamic acid and dimethylolpropionic acid that is preferred, as well as inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid.

[0058] For anionic polymers, suitable neutralizing agents include inorganic and organic bases such as sodium hydroxide, potassium hydroxide, ammonia and amines. Suitable amines include alkanolamines such as monoethanolamine, diethanolamine, dimethylaminoethanol, triethanolamine, diisopropanolamine, triisopropanolamine, and the like; alkylamines such as diethylamine, triethylamine, diisopropylamine, tributylamine and the like; trimethylamine, diethylmethylamine, methyldiethanolamine, triethanolamine, and the like. The appropriate amount of the neutralizing agent is 0.1 to 1.0 times, preferably 0.4 to 0.8 times the total theoretical neutralization equivalent.

[0059] To achieve optimum chip resistance and durability, the elastomeric polymer is curable, or thermosetting. As such, the polymer is electrodeposited with a curing or crosslinking agent such as a capped or blocked isocyanate, which is preferred for cationic compositions, or an aminoplast, which is preferred for anionic compositions.

[0060] The polyisocyanate may be fully capped with essentially no free isocyanate groups and present as a separate component or it may be partially capped and reacted with active hydrogen-containing groups, such as liydioxyl or amine groups in the elastomeric polymer backbone. Examples of suitable polyisocyanates and capping agents are those described in U.S. Patent No. 3,947,339. Fully capped polyisocyanates are described in U.S. Patent No. 3,984,299.

[0061] The polyisocyanate can be an aliphatic, cycloaliphatic or an aromatic polyisocyanate or a mixture of the two. Diisocyanates are preferred, although higher polyisocyanates can be used in place of, or in combination with, diisocyanates. Aliphatic or cycloaliphatic polyisocyanates are preferred.

[0062] Examples of suitable aliphatic diisocyanates are straight chain aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate and 1,6 hexamethylene diisocyanate. Also, cycloaliphatic diisocyanates can be employed. Examples include isophorone diisocyanate and 4,4'-methylene-bis-(cyclohexyl isocyanate). Examples of suitable aromatic diisocyanates are p-phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate and 2,4- or 2,6-toluene diisocyanate. Examples of suitable higher polyisocyanates are triphenylmethane-4,4',4"-triisocyanate, 1,2,4-benzene triisocyanate and polymethylene polyphenyl isocyanate. Biurets and isocyanurates of diisocyanates, including mixtures thereof, such as the isocyanurate of hexamethylene diisocyanate, the biuret of hexamethylene diisocyanate, and the isocyanurate of isophorone diisocyanate are also suitable.

[0063] Isocyanate prepolymers, for example, reaction products of polyisocyanates with polyols such as neopentyl glycol and trimethylol propane or with polymeric polyols such as polycaprolactone diols and triols (NCO/OH equivalent ratio greater than one) can also be used.

[0064] Any suitable aliphatic, cycloaliphatic, or aromatic alkyl monoalcohol or phenolic compound may be used as a capping agent for the capped polyisocyanate crosslinking agent in the composition of the present invention including, for example, lower aliphatic alcohols such as methanol, ethanol, and n-butanol; cycloaliphatic alcohols such as cyclohexanol; aromatic-alkyl alcohols such as phenyl carbinol and methylphenyl carbinol; and phenolic compounds such as phenol itself and substituted phenols wherein the substituents do not affect coating operations, such as cresol and nitrophenol. Glycol ethers also may be used as capping agents. Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether.

[0065] Other suitable capping agents include oximes such as methyl ethyl ketoxime, acetone oxime and cyclohexanone oxime, lactams such as epsilon-caprolactam, and amines such as dibutylamine.

[0066] Examples of other blocked polyisocyanates include triazine compounds having the formula C₃N₃(NHCOXR)₃, wherein X is nitrogen, oxygen, sulfur, phosphorus, or carbon, and R is an alkyl group having one to twelve, preferably one to four, carbon atoms, or mixtures of such alkyl groups. X is preferably oxygen or carbon, more preferably oxygen. R preferably has one to eight carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, butyl, n-octyl and 2-ethylhexyl. R preferably is a mixture of methyl and butyl groups. Such compounds, and the preparation thereof, are described in detail throughout U.S. Pat. No. 5,084,541, incorporated herein by reference. Examples of triazine compounds are tris carbamoyl triazine or 1,2,5 triazine-2,4,6 tris-carbamic acid esters. When used, the triazine curing agent is present in the film-forming composition in an amount ranging from 1 to 40 weight percent, preferably from 1 to 20 weight percent, more preferably 1 to 10 percent by weight based on the total weight of resin solids in the film-forming composition.

[0067] The polyisocyanate crosslinking agent typically is present in the thermosetting compositions of the present invention in an amount of at least 10 percent by weight, preferably at least 15 percent by weight, based on total resin solids weight of the composition. The polyisocyanate crosslinking agent typically is also present in the composition in an amount of less than 60 percent by weight, preferably less than 50 percent by weight, and more preferably less than 40 percent by weight, based on total resin solids weight of the composition. The amount of crosslinking agent present in the thermosetting composition of the present invention may range between any combination of these values, inclusive of the recited values.

[0068] The equivalent ratio of hydroxyl groups in the polymer to reactive functional groups in the crosslinking agent is typically within the range of 1:0.5 to 1.5, preferably 1.0 to 1.5.

[0069] Aminoplasts typically are obtained from the reaction of formaldehyde with an amine or amide. The most common amines or amides are melamine, urea, or benzoguanamine, and are preferred. However, condensates with other amines or amides can be used; for example, aldehyde condensates of glycoluril, which give a high melting crystalline product which is useful in powder coatings. While the aldehyde used most often is formaldehyde, other aldehydes such as acetaldehyde, crotonaldehyde, and benzaldehyde may be used.

[0070] The aminoplast contains methylol groups and preferably at least a portion of these groups are etherified with an alcohol to modify the cure response. Any monohydric alcohol may be employed for this purpose including methanol, ethanol, butanol, isobutanol, and hexanol.

[0071] Preferably, the aminoplasts are melamine-, urea-, glycouril- or benzoguanamine-formaldehyde condensates etherified with an alcohol containing from one to four carbon atoms.

[0072] The aminoplast is present in the electrodepositable composition in amounts of 5 to 60, preferably 15 to 50 percent by weight based on weight of resin solids. Adjuvant quantities of the above-described polyisocyanate crosslinker, also may be present in the composition.

[0073] Usually the thermosetting composition also will contain catalysts to accelerate the cure of the crosslinking agent with reactive groups on the polymer(s). Suitable catalysts for aminoplast cure include acids such as acid phosphates and sulfonic acid or a substituted sulfonic acid. Examples include dodecylbenzene sulfonic acid and paratoluene sulfonic acid. Suitable catalysts for isocyanate cure include organotin compounds such as dibutyltin oxide, dioctyltin oxide and dibutyltin dilaurate. The catalyst is usually present in an amount of about 0.05 to about 5.0 percent by weight, preferably 0.08 to 2.0 percent by weight, based on the total weight of resin solids in the thermosetting composition.

[0074] Optional ingredients such as pigments can be present in the elastomeric polymer-containing compositions. Particularly suitable pigments include hiding pigments such as titanium dioxide, zinc oxide, antimony oxide and organic or inorganic UV opacifying pigments such as iron oxide, transparent red or yellow iron oxide, carbon black, and phthalocyanine blue. Pigments can be present in amounts of up to 35 parts by weight or less based on 100 parts by weight of total solids of the electrodepositable composition.

[0075] Other optional ingredients are anti-oxidants, UV- absorbers and hindered amine light stabilizers, such as for example, hindered phenols, benzophenones, benzotriazoles, triazoles, triazines, benzoates, piperidinyl compounds and mixtures thereof, such as those described in U.S. Patent No. 5,260,135. These ingredients are typically added in amounts up to about 2% based on the total weight of resin solids of the electrodepositable composition. Other optional ingredients include co-solvents, coalescing aids, defoamers, plasticizers and bactericides.

[0076] The aqueous cationic or anionic polymer dispersions typically are electrodeposited onto the substrate from an electrodeposition bath having a solids content of 5 to 50 percent by weight. The bath temperature is usually 15°C to 35°C. The voltage is from 100 to 400 V (load voltage) using the substrate to be coated as a cathode in the case of the cationic polymer or as an anode in the case of the anionic polymer. The film thickness of the electrodeposited coating is not particularly restricted and can vary largely depending upon the application of the finished product, etc. However, the thickness is usually between 3 to 70 microns, particularly 15 to 35 microns in terms of cured film thickness. The baking and curing temperature of the coating film is usually from 100°C to 250°C and preferably 140°C to 200°C.

[0077] The electrocoating compositions are in the form of an aqueous dispersion. The term "dispersion" is believed to be a two-phase transparent, translucent or opaque resinous system in which the resin is in the dispersed phase and the water is in the continuous phase. The average particle size of the resinous phase is generally less than 1.0 and usually less than 0.5 microns, preferably less than 0.15 micron.

[0078] The concentration of the resinous phase in the aqueous medium is at least 1 and usually ranges from 2 to 60 percent by weight based on total weight of the aqueous dispersion.

[0079] In the process of applying the film coating, the aqueous dispersion of the electrodepositable composition is placed in contact with an electrically conductive anode and cathode. Upon passage of an electric current between the anode and cathode, an adherent film of the electrodepositable composition will deposit in a substantially continuous manner on either the anode or the cathode depending on whether the composition is anionically or cationically electrodepositable. Electrodeposition is usually carried out at a constant voltage in the range of from about 1 volt to several thousand volts, typically between 50 and 500 volts. Current density is usually between about 1.0 ampere and 15 amperes per square foot (10.8 to 161.5 amperes per square meter).

[0080] Additional film-forming layer(s) may be applied to the chip-resistant film-forming layer of the present invention. These layers include colorcoat and topcoat (clearcoat) layers. These additional layer(s) may be applied by any of the known methods for applying such coatings such as by spraying or dipping.

[0081] Illustrating the invention are the following Examples. All parts and percentages in the following Examples as well as throughout the specification are by weight unless otherwise indicated.

EXAMPLES

[0082] Several chip resistant thermosetting polyurethane electrodepositable coating compositions were prepared as shown in the following Examples.

Example 1: Part A - Preparation of Anionic Polyurethane Resins

[0083] Anionic polyurethane resins were prepared from the materials listed in Table 1. All parts and percentages are by weight unless otherwise indicated.

Table I

	All PolyTHF 1	Blend of polyTHF and JEFFAMINE	Blend of PPO2 and JEFFAMINE
	(I)	(II)	(III)
Polymeg 10003	53.34	34.66	---
Niax 10254polypropyleneglycol	---	---	34.77
Isophoronediisocyanate	31.77	33.54	33.41
Jeffamine D-20005	---	8.02	7.99
Propoxylated trimethylolpropane6 (pTMP)	---	12.97	12.89
Dimethylolpropionic acid	5.57	5.68	5.66
Trimethylolpropane	6.05	---	---
Propylene glycol	3.27	3.05	3.21
1,4 butanediol	---	2.08	2.08
Dibutyltindilaurate	0.02	0.02	0.02
Methylisobutylketone (MIBK)	25	25	25

1 polytetrahydrofuran

2 polypropylene oxide

3 polytetiahydrofuran, 1,000 molecular weight, available from Great Lakes Chemical, Corp., West Lafayette, Indiana.

4 A polyoxyethylenediamine of 2000 molecular weight available from Huntsman Corporation.

5 polypropylene glycol, 1000 molecular weight, available from Arco Chemical Co. of Newton Square, Pennsylvania as PPG-1025

6 TS-30, available from Perstorp Polyols, Inc. Toledo, Ohio.

Preparation of Example 1(I), 1(II) and 1(III)

[0084] For Example 1(I) of Table 1, isophoronediisocyanate (929.1 g, 8.37 equivalents "eq"), dibutyltindilaurate (0.58 grams "g"), and methylisobutyl ketone (145.6 g) were charged to a round bottom flask. The solution was heated to 50°C. At 50°C, Polymeg®1000 ("PolyTHF") (1,535.4 g, 3.07 eq) and MIBK (402.3 g) were added dropwise at a rate such that the temperature did not exceed 90°C. The reaction was held at 72°C for 45 minutes after the addition was complete and an isocyanate eq. wt. of 571 was obtained. At 72°C, dimethylolpropionic acid (162.8 g, 2.43 eq) and MIBK (7.5 g) were added and the reaction was held at 90°C for an anticipated isocyanate equivalent weight of 1135. At the anticipated equivalent weight ("eq wt"), propylene glycol (95.8 g, 2.52 eq), trimethylolpropane (177 g, 5.21 eq), and MIBK (168.9 g) were added and the reaction was held until no isocyanate remained (as determined by IR).

[0085] Generally the polyurethane resins of 1(II) and 1(III) were prepared in a similar manner to that of 1(I). Exceptions were that for 1(II), JEFFAMINE D-2000 and pTMP were added rather than the PolyTHF alone. Likewise for example 1(III), the polypropylene glycol, JEFFAMINE D-2000, and pTMP were added and polyTHF was not added. Also for 1(II) and 1(III), 1,4-butanediol was added in preparing the polyurethane resin.

Example 1: Part B Anionic Pigment Dispersing Resin

[0086] The following weight parts were combined:

Material	Amount in grams
Polymeg®20007	131.0
Fomrez®55-568polyester	131.0
1-methyl-2-pyrrolidinone	160.7
neopentyl glycol	10.2
Dimethylolpropionic acid	54.1
Desmodur®W9 polyisocyanate	235.1

7 poly(tetramethylene ether) glycol, Mw. = 2,000, available from Great Lakes Chemical Corp., West Lafayette, Indiana.

8 hydroxy terminated polyester, hydroxyl number 56, available from Witco Corporation, Endicott, New York.

9 methylene-bis-(4-cyclohexyl) diisocyanate, available from Bayer Corporation, Pittsburgh, Pennsylvania.

[0087] Materials 1-5 in the order and amounts indicated were charged to a reaction vessel. The mixture was then heated to 54°C. Desmodur®W polyisocyanate and 1-methyl-2-pyrrolidinone (19.0 g) were then added to the reactor at a rate such that the temperature did not exceed 85°C. After the addition of the polyisocyanate was complete, butanol (2.7 g) and dibutyltindilaurate (0.6 g) were added to the reactor. The solution was held at 85 to 90°C until a stalled isocyanate advancement was achieved (<15 units/hr., theory isocyanate equivalent weight =.1,560). After the isocyanate (NCO) advancement stalled, the resin was dispersed into deionized water (992.9 g), dimethylethanol amine (35.0 g), and ethylene diamine (15.0 g) and the dispersion was held at 75°C for 30 minutes. After the 30-minute hold, the dispersion was cooled to 50°C. At 50°C, deionized water (38.8 g) and propylene imine (6.5 g) were added. The dispersion was then heated to 60°C and held at this temperature for four hours before cooling to room temperature.

Example 1 Part C: Anionic Polyurethane Figment Paste

Part CI: Preparation of Neutralized Acid Catalyst:

[0088] Two neutralized acid catalyst formulations were made. For Example 1 Part CI(1) an amount of 284.93 grams dinonylnaphthalene sulfonic acid, Nacure 1051, available as a fifty percent dinonylnaphthalene sulfonic acid in ethyleneglycolmonobutylether, from King Industries of Noiwalk, Connecticut, were mixed with 30.32 grams of dimethylethanolamine. This gives a neutralized acid catalyst intermediate with a calculated solids of 45.19 weight percent. For Example 1 Part CI(2) 60.0 grams of dinonylnaphthalene sulfonic acid solution, Nacure 1051 and 6.68 grams of triethylamine were mixed together and diluted with 511.7 grams of deionized water to give a neutralized catalyst dispersion with a calculated solid of 5.19%.

Part CII: Preparation of Pigment Paste

[0089] The following two pigment paste formulations were prepared with the listed materials in amounts as parts by weight. These materials were mixed with a Cowles blade and then dispersed with conventional pigment dispersing equipment to a Hegman reading of 7.5+:

	CII(1)	CII(2)
Solvent free acrylic grind resin10	-----	212.2
Acid catalyst of Example 1CI(1)	55.1	-----
Anionic Pigment Dispersing Resin of Example 1B	766.4	----
triethylamine	-----	17.5
Carbon Black11a(11b)	27.9	15.5
Titanium Dioxide12a(12b)	634.7	634.7
Transparent Red Iron Oxide13	74.6	84.9
Phthalo Blue14	9.4	10.6
Deionized water	200	480

10 Resin prepared with materials as described in Example A of U.S. Patent 5,530,043 to 100 percent solids.

11a Raven 410 and 11b Raven 1200 both available from Columbian Chemicals Company, Atlanta, Georgia.

12a R-900 and 12b R-960-38 both available from DuPont de Nemours Company, Delaware.

13 1030-AC-1005 available from Cookson Matthey of Jacksonville, Florida:

14 248-0061 available from Sun Chemical, Inc., Linden, New Jersey.

[0090] For Example CII(1) after dispersion, the dispersing mill was rinsed with a small amount of deionized water. The resulting pigment paste had a measured solids (60 minutes at 110°C) of 57.3 percent.

Example 1 Part D: Preparation of Electrodepositable

Thermosetting Anionic Polyurethane Formulations

[0091] The following formulations were made using polyurethane backbones from Example 1 Part A as indicated in Table 2, crosslinkers, and modifiers:

Table 2

	All PolyTHF	Blend of polyTHF and Jeffamine	All poly PPO (polypropyleneoxide)	All polyTHF resin plus free PPO triol
Formulation	D1	D2	D3	D4
Resin from Example 1A (80% solids in MIBK)	(I)	(II)	(III)	(I)
Amount of 1A Resin	268.8	268.8	268.8	237.5
Cymel 113515	20	20	20	20
Cymel 112316	15	15	15	15
Polypropyleneoxide triol17	---	---	---	25
Dimethylethanolamine	3.83	3.83	3.83	3.83
Deionized water	550	550	550	550
Amount of flexibilizing segment	47.2	49.2	49.2	52.0
Ratio Polytetrahydrofuran to polypropylene oxide	∞	1.65/1	0	4.06

15 methoxy/n-butoxy melamine formaldehyde resins available from Cytec Industries Inc. West Patterson, New Jersey.

16 methylated ethylated benzoguanamine resins available from Cytec Industries Inc.

17 LHT-240, 720 molecular weight polypropyleneoxide triol available from Arco Chemical Co. of Newton Square, Pennsylvania.

Formulations D1-D4 were made using the following procedure:

[0092] The resin, crosslinkers, and amine were weighed into a quart sized stainless steel beaker, and the beaker placed in a water bath maintained at 80°C. The mixtures were stirred with an air motor and flat pitched propeller blade until homogeneous. Under continuous stirring, 550 grams of deionized water was added slowly to form an aqueous dispersion. After forming the aqueous dispersion, the heat to the water bath was turned off, and the mixtures were allowed to cool. The mixtures were transferred to open one gallon (3,8 l) plastic containers and stirred overnight with magnetic stirring bars. After stirring overnight to allow most of the ketone solvent to evaporate, an additional 3490 grams of deionized water, along with 75.1 grams of pigment paste from Example 1 Part CII(1) were added to complete the electrocoat bath formulations.

[0093] The calculation of the amount of flexibilizing segment in Table 2 of Example 1 Part D was determined in the following manner. The weights of the active hydrogen-containing polymers are summed. Accordingly, the weights of the following molecules are summed: polytetrahydrofuran, polyether diols, polyether diamines and polyether plasticizers. For the total resins solids, all materials contributing to resin solids are summed, with the proviso that for the Cymel 1123 and Cymel 1135 amine-formaldehyde resins, a weight loss upon curing is estimated. A weight loss for both Cymel 1123 and Cymel 1135 is estimated to be 20%, giving them estimated solids in a baked film of 80%.

[0094] As a sample calculation of flexibilizing segment content, the calculation for Formulation D1 is as follows:

Solid resin materials from resin	215 grams
Cymel 1135 (20 grams x .8)	16 grams
Cymel 1123 (15 prams x .8)	12 grams
Total	243 grams

Flexibilizing segments: 215 grams of resins solids x 53.34 % Polymeg 100 = 114.7 grams of Polymeg 1000. 114.7/243 = 47.2 % as the amount of flexibilizing segment. The other amounts of flexibilizing segment for the other formulations were calculated in a like manner.

[0095] The determination of the weight loss upon curing of amine-formaldehyde resins can depend on many factors such as bake schedule, amount of acid catalysis, and amount of available co-reactants. Nevertheless, but can be estimated from a supplier's reported range of equivalent weight. The equivalent weight of Cymel 1123 is reported to range from 130 to 190 grams per mole of reaction site. The molecular weight of Cymel 1123 benzoguanamine monomer is estimated as 391 by assuming equal moles of the alkylation alcohols, methanol and ethanol. Calculating a weight loss for two moles of methanol yields a calculated weight loss of 15.8 %. Calculating a weight loss for two moles of methanol and one mole of ethanol yields a calculated weight loss of 27.4%. The calculations are only rough estimates of how an amine-formaldehyde resin will cure in a particular formulation. An estimate of 20% weight loss is applied to both Cymel 1123 and Cyme I 1135 in the examples.

Examples 2 and 3

[0096] Two thermosetting anionic polyurethane electrodepositable compositions were prepared from the formulations shown in Table 3 where the amounts of the components are given in parts by weight.

Table 3

Charge	Material	Example 2	Example 3
1	Isophoronediisocyanate	922.4	461.6
2	Dibutyltindilaurate	0.55	0.28
3	MIBK	253.7	90.2
	Hold Temperature °C	70	50
4	Polymeg 1000	953.3	586.8
5	MIBK	238.3	146.7
6	1,4 butanediol	57.3	12.8
7	MIBK	---	11.3
8	Jeffamine D-2000	220.5	110.3
8A	MIBK	15	7.5
9	Dimethylolpropionic acid	156.3	78.9
10	MIBK	127.5	7.5
10A	propylene glycol	83.9	21.8
11	Propoxylated trimethylolpropane (pTMP)	356.9	---
11	Trimethylolpropane	---	125.9
12	MIBK	71.1	75
13 14	MIBK	69.9	11.3
	Dimethylethanolamine	52	---
14A	Triethylamine	---	44.6
15	Paraplex WP-118	---	73.6
15A	Cymel 1123	191.9	---
16	Cymel 1135	256.2	---
16A	Cymel 1170		370.1
17	deionized water	2637.4	1536.6
18	deionized water	2475.14	1180.9

18 Propoxylated cresol plasticizer available from C.P. Hall Company, Chicago, Illinois.

Preparation of Anionic Polyurethane Formulation Stripped of Solvent

[0097] For Examples 2 and 3, the components listed in Table 3 were combined in a similar manner. Any difference for Example 3 from Example 2 is indicated in the following description. The isophoronediisocyanate, dibutyltindilaurate, and MIBK were charged to a reaction vessel. The mixture was heated to 70°C (50°C) under a nitrogen blanket with agitation. The POLYNIEG® 1000, MIBK, 1,4-butanediol and JEFFAMINE® D-2000 were added slowly, at a rate that kept the reaction temperature at or below 90°C. For Example 3 the JEFFAMINE® D-2000 was added slowly with a MIBK rinse to the three other materials after they were combined at a rate to keep the temperature below 90°C along with an MIBK rinse and held at 75°C for 27 minutes. For Example 2 an MIBK rinse was also subsequent to the addition of JEFFAMINE® D-2000 polyamine. The reaction was held at 75°C for 60 (27) minutes. An isocyanate equivalent weight (eq. wt.) of 556 (570) was obtained. Dimethylolpropionic acid was added followed by a rinse of MIBK, and the reaction mixture heated to 88°C. When the isocyanate eq. wt. reached 1185, propylene glycol, and propoxylated trimethylolpropane, for Example 2, or trimethylolpropane, for Example 3, and MIBK were added to the reaction mixture followed by a rinse with MIBK. The reaction mixture was held at 100°C until the isocyanate was consumed (as determined by IR).

[0098] For Example 2, the reaction mixture was cooled to 93°C. For Example 3 the reaction was discontinued over night and heated the next day to 95°C. Dimethylethanolamine, and either Cymel® 1123 and Cymel® 1135 (or for Example 3 Paraplex WP-1 and Cymel® 1170) were added and mixed for 10 minutes. For Example 2, the first addition of deionized water was made over one hour, and the dispersion was cooled to 60°C. This temperature was held for 30 minutes before the second addition of deionized water was made over 60 minutes while maintaining a temperature of 60°C. For Example 3 the first addition of deionized water was made to 93% of the above reaction over 34 minutes and the reaction was allowed to mix for 24 minutes. The second addition of deionized water was made over 47 minutes. Both dispersions were vacuum stripped at 60°C to remove solvent.

[0099] For Example 2 the composition was filtered and adjusted with deionized water to a solids content of 34.1 (35.1 weight percent for Example 3). For Example 2, 953.2 grams of this filtered resin was blended with 97.63 grams of the pigment paste of Example 1 Part CII(1) and 2.75 liters of deionized water to complete the electrocoat bath formulation.

[0100] For Example 3 the anionic thermosetting polyurethane electrodepositable composition was prepared from the polyurethane of Example 3 and the catalyst dispersion of Example 1 Part CI(2) and the pigment paste of Example CII(2). This was performed under continuous agitation from a magnetic stirring bar in a plastic, one gallon sized container. 880.7 grams of the polyurethane resin of Example 3 was diluted with 1.5 liters of deionized water and mixed with 24.66 grams of the catalyst dispersion of Example 1 Part CI(2), diluted with 100 grams of deionized water, 70.5 grams of the pigment paste of Example 1 Part CII(2), diluted with 50 grams of deionized water. Deionized water was added to increase the volume of the electrocoat bath to 3.5 liters, completing the formulation.

Example 4: Preparation of Cationic Thermosetting Polyurethane

Electrodepositable Composition

Example 4 Part A: Preparation of Cationic Polyurethane Resin

[0101] Isophoronediisocyanate (1200.6 g, 10.82 eq.), methylisobutyl ketone (520.2 g), and dibutyltindilaurate (0.6 g) were charged to a round bottom flask. The mixture was heated to 30°C. Trimethylolpropane (125.1 g, 2.80 eq.) was then added to the solution. After the addition, the temperature rose to 73°C. Caprolactam (382.9 g, 3.38 eq.) and MIBK (40.0 g) were added to the flask. The mixture was maintained at 85°C until an isocyanate (NCO) eq. wt. of 490 was obtained. TERETHANE®650, polytetrahydrofuran of 650 molecular weight available from DuPont. "PolyTHF" (707.9 g, 2.21 eq.) and MIBK (275.7 g) were then added to the flask. The addition was made at a rate such that the temperature was maintained below 90°C. After the addition was complete, the temperature was allowed to drift down to 65°C. At 65°C, JEFFAMINE®D-2000 (437.0 g, 0.44 eq.), and MIBK (40.0 g) were added and the mixture was held for 15 minutes. After the hold, an NCO eq. wt. of 1974 was obtained. Diethanolamine (87.0 g, 0.83 eq.) and 125g aminopropyldiethanolamine (125.2 g, 0.77 eq.) were then added to the reaction mixture. The solution was held at 80°C until no NCO was present as determined by IR analysis. After the isocyanate was consumed, 31g SURFYNOL® GA surfactant (30.7 g) and MIBK (40.0 g) were added and the solution was mixed for 15 minutes. The resin was then dispersed into deionized water (1,666.0 g) and dimethylolpropionic acid (82.9 g, 0.62 eq). The resin was further thinned with deionized water (3,303.0 g), resulting in a final dispersion at 36.5% solids. The dispersion was subsequently vacuum stripped at 60°C to remove solvent.

Example 4 Part B

[0102] The following materials were mixed with a Cowles blade and then dispersed with conventional pigment dispersing equipment to a Hegman reading of 7+:

Epoxy grind resin19	1466.1
Deionized water	294.7
Titanium Dioxide20	1166.4
Transparent Red Iron Oxide21	137.2
Phthalo Blue22	17.2
Carbon Black23	51.5

19 Sulfonium-quaternary ammonium type described in U.S. Patent No. 5,130,004 (PPG Industries, Inc., Johnson & McCollum) with a solids content of 31.2 percent

20 See footnote 11a.

21 See footnote 12.

22 See footnote 13.

23 See footnote 10a.

The resulting pigment paste had a calculated solid content of 58.4 weight percent.

Example 4 Part C: Cationic Polyurethane Electrocoat Composition

[0103] 1067.9 grams of the resin of Example 4 Part A was blended with 105.8 grams of the pigment paste of Example 4 Part B and diluted with water to a total volume of 3.8 liters.

Example 5: Preparation of a Cationic Thermosetting Polyurethane Electrodepositable Composition

[0104] A resin was prepared from the following ingredients.

Ingredients	Solution weight (grams)
Dibutyltindilaurate	0.78
Isophorone Diisocyanate	1665.0
Methylisobutyl Ketone	520.0
Trimethylol Propane	232.0
Terethane 65024	1010.9
Methylisobutyl Ketone	302.7
Caprolactam	402.4
Methylisobutyl Ketone	50.0
Jeffamine D2000	631.5
Methylisobutyl Ketone	50.0
Aminopropyldiethanolamine	294.5
Methylisobutyl Ketone	40.0
Tinuvin 90025	5.3
Methylisbutyl Ketone	5.3
Tinuvin 123 26	5.3
Methylisobutyl Ketone	5.3
Dimethylolpropionic Acid	137.6
Deionized Water	2614.7
Deionized Water	797.3
Deionized Water	2192.7
Deionized Water	2325.6

24A polytetrahydrofuran resin of 650 molecular weight available from DuPont.

25An ultraviolet light absorber available from Ciba-Geigy Corporation.

26A hindered amine light stabilizer available from Ciba-Geigy Corporation.

[0105] The dibutyltindilaurate, isophrone diisocyanate, and methylisobutyl ketone (520.0gms.) were charged to a round-bottom flask and heated to 25°C. Trimethylolpropane was added, and the mixture was allowed to exotherm to 80°C and held at that temperature for 15 minutes. The Terethane 650 and methylisobutyl ketone (302.7 gms) were added over 30 minutes, holding the temperature under 90°C, then holding the mixture at 80°C for 15 minutes. The caprolactam and methylisobutyl ketone (50.0 gms) were added, allowed to exotherm to 90°C, then held at 90°C for 2 hours. The mixture was cooled to 75°C, and the JEFFAMINE D-2000 and methylisobutyl ketone (50.0 gms) were added and held at 15 minutes at 70°C. The aminopropyldiethanolamine and methylisobutyl ketone (40.0 gms) were added and held for 30 minutes at 80°C. The Tinuvin 900 slurried with 5.3 gms MIBK, followed by the Tinuvin 123 slurried with 5.3 gms MIBK, were added and the mixture was held at 80°C for 15 minutes. The mixture was then poured into a room temperature solution of dimethylolpropionic acid in deionized water (2614.7 gm), and stirred for 30 minutes. 797.3 gm more deionized water was added and stirred for 15 minutes. 2192.7 gm more deionized water was added and stirred for 15 minutes. 2329.6 gm. more deionized water was added and stirred for 15 minutes. The dispersion was vacuum stripped at 60°C to remove solvent and deionized water was added back resulting in a final solids of 34.2%.

Ingredients	Solution weight (grams)
2-ethylhexanol half-capped toluene diisocyanate, 95% in MIBK	320
dimethylethanolamine (DMEA)	87.2
aqueous lactic acid solution, 88%	117.6
2-butoxyethanol	39.2

[0106] The 2-ethylhexanol half-capped toluene diisocyanate was added to the DMEA in a suitable reaction vessel at room temperature. The mixture exothermed and was stirred for one hour at 80°C. The aqueous lactic acid solution was then charged followed by addition of 2-butoxyethanol. The reaction mixture was stirred for about one hour at 65°C to form the quaternizing agent.

[0107] The pigment grinding vehicle was prepared as follows:

Ingredients	Solution weight (grams)
EPON 82927	710
Bisphenol A	289.6
2-ethylhexanol half-capped toluene diisocyanate, 95% in MIBK	320
quaternizing agent described above	496.3
deionized water	71.2
2-butoxyethanol	1205.6

27Diglycidyl ether of Bisphenol A available from Shell Oil and Chemical Co.

[0108] The EPON 829 and Bisphenol A were charged under a nitrogen atmosphere to a suitable reactor and heated to 150 to 160°C to initiate an exotherm. The reaction mixture was permitted to exotherm for one hour at 150 to 160°C. The reaction mixture was then cooled to 120°C and the 2-ethylhexanol half-capped toluene diisocyanate added. The temperature of the reaction mixture was held at 110 to 120°C for one hour followed by the addition of the 2-butoxyethanol. The reaction mixture was then cooled to 85 to 90°C, homogenized, and charged with water followed by the quaternizing agent. The temperature of the reaction mixture was held at 80 to 85°C until an acid value of about 1 was obtained. The final product had a solids content of about 56.0%.

[0109] A dibutyltinoxide catalyst paste was prepared from the following ingredients.

Ingredients	Solution weight (grams)
Dibutyltinoxide	300.0
Pigment Grinding Vehicle	214.3
Deionized Water	398.1

The paste was sand-milled to a Hegman 7.

[0110] A pigment paste was prepared from the following ingredients.

Ingredients	Solution weight (grams)
Epoxy Grind Resin28	1582.4
Deionized Water	90.55
Titanium Dioxide29	1278.75
Transparent Yellow Iron Oxide30	150.0
Carbon Black31	55.5
Dibutyltinoxide Paste	47.9

28Sulfonium-quaternary ammonium type described in U.S. Patent No. 5,130,004 with a solids content of 31.2%.

29Available from DuPont as R900.

30Available from Cookson-Matthey as Trans-Oxide Yellow GS 10-30-AC-0544.

31Available from Columbian Chemicals Co. as Raven 410.

[0111] The pigment paste was sand-milled to a Hegman 7.

[0112] A cationic electrodeposition bath was prepared from the following ingredients.

Ingredients	Solution weight (grams)
Resin	2309.2
Pigment Paste	210.7
Deionized Water	5080.1

Example 6: Preparation of a Cationic Thermosetting Polyurethane-Polyurea Resin

[0113] A cationic polyurethane-polyurea resin was prepared from the following ingredients.

Ingredients	Solution weight (grams)
Dibutyltindilaurate	0.78
Isophorone Diisocyanate	1665.0
Methylisobutyl Ketone	545.0
Trimethylol Propane	267.8
Caprolactam	440.8
Methylisobutyl Ketone	25.0
PMDA 100032	1016.0
Methylisobutyl Ketone	400.0
JEFFAMINE D2-000	792.1
Methylisobutyl Ketone	50.0
Aminopropyldiethanolamine	305.3
Methylisobutyl Ketone	100.0
Tinuvin 900 33	5.6
Methylisbutyl Ketone	5.0
Tinuvin 123 34	5.6
Methylisobutyl Ketone	5.0
Dimethylolpropionic Acid	121.3
Deionized Water	2267.3
Deionized Water	717.4
Deionized Water	1972.7
Deionized Water	1409.1

32An amine terminated polytetramethylene glycol prepared by cyanoethylation followed by hydrogenation of polytetramethylene glycol polytetrahydrofuran resin of 1000 molecular weight; purchased from Air Products Corporation.

33An ultraviolet light absorber available from Ciba-Geigy Coiporation.

34A hindered amine light stabilizer available from Ciba-Geigy Corporation.

[0114] The dibutyltindilaurate, isophrone diisocyanate, and methylisobutyl ketone (545.0 gms.) were charged to a round-bottom flask and heated to 25°C. Trimethylolpropane was added, and the mixture was allowed to exotherm to 80°C and held at that temperature for 1 hour. The caprolactone and methylisobutyl ketone (25.0 gms) were added and the mixture held at 85-90°C for 2 hours at which point NCO equivalent weight was 575. The mixture was cooled to 75°C and the PMDA 1000 was then added over 30 minutes controlling the temperature below 80°C, methylisobutyl ketone (400.0 gms) was added as a rinse. The mixture was then held at 80°C for 15 minutes. The JEFFAMINE D-2000 and methylisobutyl ketone (50.0 gms) were added and held at 15 minutes at 80°C. The aminopropyldiethanolamine and methylisobutyl ketone (50.0 gms) were added and held for 30 minutes at 80°C. The Tinuvin 900 slurried with 5.3 gm MIBK followed by Tinuvin 123 slurried with 5.3 gm MIBK were added followed by and the mixture was held at 80°C for 15 minutes. 4785 grams of the mixture was then poured into a room temperature solution of dimethylolpropionic acid in deionized water (2267.3 gm), and stirred for 30 minutes. 717.43 gm more deionized water was added and stirred for 15 minutes. 1972.7 gm more deionized water was added and stirred for 15 minutes. 1409.1 gm. more deionized water was added and stirred for 15 minutes. The dispersion was vacuum stripped at 60°C to remove solvent and deionized water was added back resulting in a final solids of 34.2%.

Example 7: Testing of Elastomeric Electrocoat Composition

[0115] A cationic polyurethane electrocoat composition was prepared as described in Example 5 and was coated on various substrates, as indicated below.

[0116] The treated substrates were subjected to chip-resistance and corrosion-resistance tests, as follows.

[0117] For Velociball testing, topcoated panels were stored in a freezer at -20°C for at least two hours, and then shot with a 2 or 3 mm chrome steel ball at a velocity of 75, 95, or 155 miles per hour (121, 153, or 249 km/hour). The ball impacted the coated test panel at 90°C, or perpendicular to the surface. After removing from the freezer, raised and loosened portions of the paint system were removed with a sharp tool. The circle of damage was measured in millimeters and the results reported in diameter of damage.

[0118] The Gravel-O-Meter tests were performed according to the protocol described in SAE J400, rev. 1/85, and were run at 0°F (-17.8°C).

[0119] The cycle B corrosion tests were performed according to General Motors Engineering Standard 9540P, Method B.

[0120] The results of testing performed on Samples 1-14 may be found in Table 5, below.

[0121] These data indicate the feasibility of substituting a single layer of the elastomeric coating composition of the present invention for two layers of an electrocoat plus a primer/surfacer as is known in the art. The use of the composition of the present invention affords significant chip-resistance and does not significantly reduce corrosion resistance when applied to corrosion-resistant substrates (samples 1-5).

Claims

1. A coated article, comprising:

a. a corrosion-resistant electrically conductive substrate that is free of an electrodeposited coating; and

b. an electrodeposited film-forming composition applied to at least a portion of a surface of the corrosion-resistant electrically conductive substrate, the film-forming composition comprising a curable electrodepositable elastomeric polymer, said polymer comprising the reaction product of a polyisocyanate, and an active hydrogen-containing polymer selected from a polyether polyamine, and/or a mixture of a polyether polyamine,
and a polyester polyol and/or a polyether polyol.

2. The coated article of claim 1 in which the polyether polyamine comprises a polyoxyalkylene polyamine or a mixture of a polyoxyalkylene polyamine and a polyoxyalkylene polyol.

3. The coated article of claim 1 in which the elastomeric polymer is essentially aliphatic.

4. The coated article of claim 1 in which the polyisocyanate is an aliphatic or cycloaliphatic polyisocyanate.

5. The coated article of claim 1 in which the polyisocyanate is selected from the group consisting of isophorone diisocyanate. 1,6-hexamethylene diisocyanate, 4, 4'-diisocyanatodicyclohexyl methane and isocyanurates thereof.

6. The coated article of claim 1 in which the polyether polyamine is selected from the group consisting of a polyoxytetramethylene diamine, a polyoxypropylene polyamine, a polyoxyethylene polyamine and mixtures thereof.

7. The coated article of claim 1 in which the polyether polyamine is (A) a polyoxytetramethylene diamine.

8. The coated article of claim 7 in which the polyether polyamine further comprises (B) a polyoxypropylene polyamine.

9. The coated article of claim 8 in which the weight ratio of (A) to (B) ranges_from 0.5 to 10:1.

10. The coated article of claim 1 in which the polyether polyamine comprises a mixture of (i) a polyoxytetramethylene diamine and (ii) at least one of a polyoxypropylene diamine and a polyoxyethylene diamine in which the weight ratio of (i) to (ii) ranges from 0.5 to 10:1.

11. The coated article of claim 1 in which the polyether polyamine is selected from the group consisting of polyoxypropylene diamines, polyoxyethylene-propylene diamines and polyoxytetramethylene diamines.

12. The coated article of claim 1 in which the polyether polyamine has a glass transition temperature of 0°C or less and a number average molecular weight ranging from 400 to 4000.

13. The coated article of claim 1 in which the polyether polyamine is present in the elastomeric polymer in an amount of at least 30

14. The coated article of claim 1, in which the curable elastomeric polymer comprises the reaction product of i) a polyisocyanate, ii) a polyether polyamine having a number average molecular weight greater than 400, and iii) an active hydrogen-containing compound having a number average mol ecul ar weight below 400.

15. The coated article of claim 1 in which the elastomeric polymer contains active hydrogen-containing groups and the electrodeposited film-forming composition comprises a curing agent having groups that are reactive with the active hydrogens.

16. The coated article of claim 15 in which the curing agent is selected from the group consisting of an aminoplast and a capped polyisocyanate.

17. The coated article of claim 15 in which the curing agent is a capped polyisocyanate which is capped with a capping agent selected from the group consisting of caprolactam and dibutylamine.

18. The coated article of claim 15 in which the curing agent is a capped polyisocyanate that is provided integral with the elastomeric polymer backbone.

19. The coated article of claim 1 in which the elastomeric polymer contains active hydrogen-containing groups and ionic salt groups or groups that can be converted into ionic salt groups.

20. The coated article of claim 19 in which the ionic salt groups or groups that can be converted into an ionic salt group are selected from the group consisting of carboxyl groups and amino groups.

21. The coated article of claim 1 in which the film-forming composition further comprises an opacifying pigment.

22. The coated article of claim 21 in which the opacifying pigment is selected from the group consisting of non-transparent iron oxides and transparent iron oxides.

23. The coated article of claim 1 in which the film-forming composition further comprises a hindered amine light stabilizer.

24. The coated article of claim 1 in which the film-forming composition is a cationic electrodepositable film-forming composition.

25. The coated article according to claim 1. wherein the coated article further comprises a non-insulating layer of a corrosion-resistant coating positioned between the electrically conductive substrate and the coating composition.

26. The coated article of claim 1 in which at least a portion of the corrosion-resistant substrate is zinc or zinc alloy surface treated steel.

27. The coated article of claim 26 in which at least a portion of a surface of the substrate is coated with a non-insulating layer of a zinc-rich or iron phosphide-rich organic film-forming composition.

28. The coated article of any of claims 26 or 27 in which at least a portion of a surface of the substrate is further treated with a zinc phosphate pretreatment solution.

29. The coated article of any of claims 26 or 27 in which at least a portion of a surface of the substrate is coated with non-insulating layer of a corrosion-resistant coating comprising a Group IIIB or IVB metal compound or mixtures thereof.

30. The coated article of claim 1 in which at least a portion of the corrosion-resistant substrate is aluminum or an alloy thereof.

31. The coated article of claim 30 in which at least a portion of the surface of the substrate is coated with a non-insulating layer of a zinc-rich or iron phosphide-rich organic film-forming composition.

32. The coated article of any of claims 30 or 31 in which at least a portion of the surface of the substrate is coated with a non-insulating layer of a phosphatized epoxy composition.

33. The coated article of any of claims 30 or 31 in which at least a portion of a surface of the substrate is further treated with a zinc phosphate pretreatment solution.

34. The coated article of claim 1 in which one or more additional film-forming layers is applied to an exposed surface of the layer comprising the electrodeposited film-forming composition.

35. The coated article of claim 1 in which the cured electrodeposited film-forming composition includes at least 0.5 meq polyurea linkages per gram of cured film.

36. The coated article of claim 35 in which the cured electrodeposited coating composition includes at least 0.6 meq polyurea linkages per gram of cured film.

37. The coated article of claim 35 in which the cured electrodeposited coating composition includes at least 1.0 meq polyurea linkages per gram of cured film.

38. A process for electrocoating a corrosion-resistant electrically conductive substrate, which is free of an electrodeposited coating, comprising the step of electrodepositing a coating composition onto a surface of the electrically conductive substrate, the coating composition comprising a curable elastomeric polymer.

39. The process of claim 38 in which the curable elastomeric polymer is a polyurethane or polyurea which comprises the reaction product of a polyisocyanate and an active hydrogen-containing elastomeric polyester or polyether.

40. The process of claim 39 in which the active hydrogen-containing polyester or polyether is selected from the group consisting of polyoxyalkylene polyols, polyoxyalkylene polyamines and mixtures thereof.

41. The process of claim 39 in which the active hydrogen-containing polyester or polyether polymer is selected from the group consisting of a polyoxytetramethylene diol or diamine, a polyoxypropylene diol or diamine, a polyoxyethylene diol or diamine and mixtures thereof.

42. The process of claim 39 in which the active hydrogen-containing polyester or polyether is selected from the group consisting of polyoxypropylene diamines, polyoxyethylene-propylene diamines and polyoxytetramethylene diamines.

43. The process of claim 40 in which the active hydrogen-containing polyester or polyether has a glass transition temperature of 0°C or less and a number average molecular weight of 400-4000.

44. The process of claim 38 in which the electrodeposited coating composition, when cured, includes at least 0.5 meq polyurea linkages per gram of cured film.

Ansprüche

1. Beschichteter Gegenstand, der

a. ein korrosionsbeständiges, elektrisch leitfähiges Substrat, das frei von einer elektrophoretisch abgeschiedenen Beschichtung ist, und

b. eine elektrophoretisch abgeschiedene, filmbildende Zusammensetzung , die auf wenigstens einen Teil einer Oberfläche des korrosionsbeständigen, elektrisch leitfähigen Substrats aufgebracht ist, wobei die filmbildende Zusammensetzung ein härtbares, elektrophoretisch abscheidbares, elastomeres Polymer enthält und dieses Polymer das Reaktionsprodukt eines Polyisocyanats und eines aktiven Wasserstoff enthaltenden Polymers, ausgewählt aus einem Polyetherpolyamin und/oder einer Mischung eines Polyetherpolyamins und eines Polyesterpolyols und/oder eines Polyetherpolyols, ist,

aufweist.

2. Beschichteter Gegenstand nach Anspruch 1. bei dem das Polyetherpolyamin ein Polyoxyalkylenpolyamin oder eine Mischung eines Polyoxyalkylenpolyamins und eines Polyoxyalkylenpolyols enthält.

3. Beschichteter Gegenstand nach Anspruch 1, bei dem das elastomere Polymer im Wesentlichen aliphatisch ist.

4. Beschichteter Gegenstand nach Anspruch 1, bei dem das Polyisocyanat ein aliphatisches oder cycloaliphatisches Polyisocyanat ist.

5. Beschichteter Gegenstand nach Anspruch 1, bei dem das Polyisocyanat ausgewählt ist aus der Gruppe bestehend aus Isophorondiisocyanat, 1,6-Hexamethylendiisocyanat, 4,4'-Diisocyanatodicyclohexylmethan und Isocyanuraten davon.

6. Beschichteter Gegenstand nach Anspruch 1, bei dem das Polyetherpolyamin ausgewählt ist aus der Gruppe bestehend aus einem Polyoxytetramethylendiamin, einem Polyoxypropylenpolyamin, einem Polyoxyethylenpolyamin und Mischungen davon.

7. Beschichteter Gegenstand nach Anspruch 1, bei dem das Polyetherpolyamin (A) ein Polyoxytetramethylendiamin ist.

8. Beschichteter Gegenstand nach Anspruch 7, bei dem das Polyetherpolyamin zusätzlich (B) ein Polyoxypropylenpolyamin enthält.

9. Beschichteter Gegenstand nach Anspruch 8, bei dem das Gewichtsverhältnis von (A) zu (B) im Bereich von 0,5 bis 10:1 liegt.

10. Beschichteter Gegenstand nach Anspruch 1, bei dem das Polyetherpolyamin eine Mischung (i) eines Polyoxytetramethylendiamins und (ii) wenigstens eines von einem Polyoxypropylendiamin und einem Polyoxyethylendiamin enthält und das Gewichtsverhältnis von (i) zu (ii) im Bereich von 0,5 bis 10:1 liegt.

11. Beschichteter Gegenstand nach Anspruch 1, bei dem das Polyetherpolyamin ausgewählt ist aus der Gruppe bestehend aus Polyoxypropylendiaminen, Polyoxyethylenpropylendiaminen und Polyoxytetramethylendiamin.

12. Beschichteter Gegenstand nach Anspruch 1, bei dem das Polyetherpolyamin eine Glasübergangstemperatur von 0°C oder weniger und ein zahlenmittleres Molekulargewicht im Bereich von 400 bis 4000 aufweist.

13. Beschichteter Gegenstand nach Anspruch 1, bei dem das Polyetherpolyamin in dem elastomeren Polymer in einer Menge von wenigstens 30 Gew.-% der Reaktanten, die zur Herstellung des elastomeren Polymers verwendet werden, vorhanden ist.

14. Beschichteter Gegenstand nach Anspruch 1, bei dem das härtbare elastomere Polymer das Reaktionsprodukt von i) einem Polyisocyanat, ii) einem Polyetherpolyamin mit einem zahlenmittleren Molekulargewicht von mehr als 400 und iii) einer aktiven Wasserstoff enthaltenden Verbindung mit einem zahlenmittleren Molekulargewicht von unter 400 enthält.

15. Beschichteter Gegenstand nach Anspruch 1, bei dem das elastomere Polymer aktiven Wasserstoff enthaltende Gruppen enthält und die elektrophoretisch abgeschiedene, filmbildende Zusammensetzung ein Härtungsmittel enthält, das Gruppen aufweist, die mit den aktiven Wasserstoffatomen reaktiv sind.

16. Beschichteter Gegenstand nach Anspruch 15, bei dem das Härtungsmittel ausgewählt ist aus der Gruppe bestehend aus einem Aminoplast und einem verkappten Polyisocyanat.

17. Beschichteter Gegenstand nach Anspruch 15, bei dem das Härtungsmittel ein verkapptes Polyisocyanat ist, das mit einem Verkappungsmittel ausgewählt aus der Gruppe bestehend aus Caprolactam und Dibutylamin verkappt ist.

18. Beschichteter Gegenstand nach Anspruch 15, bei dem das Härtungsmittel ein verkapptes Polyisocyanat ist, das integral mit dem elastomeren Polymergerüst zur Verfügung gestellt wird.

19. Beschichteter Gegenstand nach Anspruch 1, bei dem das elastomere Polymer aktiven Wasserstoff enthaltende Gruppen und ionische Salzgruppen oder Gruppen, die in ionische Salzgruppen überführt werden können, enthält.

20. Beschichteter Gegenstand nach Anspruch 19, bei dem die ionischen Salzgruppen oder Gruppen, die in ionische Salzgruppen überführt werden können, ausgewählt sind aus der Gruppe bestehend aus Carboxylgruppen und Aminogruppen.

21. Beschichteter Gegenstand nach Anspruch 1, bei dem die filmbildende Zusammensetzung zusätzlich ein opazifierendes Pigment enthält.

22. Beschichteter Gegenstand nach Anspruch 21, bei dem das opazifierende Pigment ausgewählt ist aus der Gruppe bestehend aus nichttransparenten Eisenoxiden und transparenten Eisenoxiden.

23. Beschichteter Gegenstand nach Anspruch 1, bei dem die filmbildende Zusammensetzung zusätzlich einen Lichtstabilisator aus einem gehinderten Amin enthält.

24. Beschichteter Gegenstand nach Anspruch 1, bei dem die filmbildende Zusammensetzung eine kationische, elektrophoretisch abscheidbare, filmbildende Zusammensetzung ist.

25. Beschichteter Gegenstand nach Anspruch 1, wobei der beschichtete Gegenstand zusätzlich eine nichtisolierende Schicht aus einer korrosionsbeständigen Beschichtung enthält, die zwischen dem elektrisch leitfähigen Substrat und der Beschichtungszusammensetzung angeordnet ist.

26. Beschichteter Gegenstand nach Anspruch 1, bei dem wenigstens ein Teil des korrosionsbeständigen Substrats Zink oder mit einer Zinklegierung oberflächenbehandelter Stahl ist.

27. Beschichteter Gegenstand nach Anspruch 26, bei dem wenigstens ein Teil einer Oberfläche des Substrats mit einer nichtisolierenden Schicht aus einer zinkreichen oder eisenphosphidreichen, organischen, filmbildenden Zusammensetzung beschichtet ist.

28. Beschichteter Gegenstand nach einem der Ansprüche 26 oder 27, bei dem wenigstens ein Teil einer Oberfläche des Substrats zusätzlich mit einer Zinkphosphat-Vorbehandlungslösung vorbehandelt ist.

29. Beschichteter Gegenstand nach einem der Ansprüche 26 oder 27, bei dem wenigstens ein Teil einer Oberfläche des Substrats mit einer nichtisolierenden Schicht einer korrosionsbeständigen Beschichtungszusammensetzung, die eine Gruppe-IIIB- oder -IVB-Metallverbindung oder Mischungen davon enthält, beschichtet ist.

30. Beschichteter Gegenstand nach Anspruch 1, bei dem wenigstens ein Teil des korrosionsbeständigen Substrats Aluminium oder eine Legierung davon ist.

31. Beschichteter Gegenstand nach Anspruch 30, bei dem wenigstens ein Teil der Oberfläche des Substrats mit einer nichtisolierenden Schicht aus einer zinkreichen oder eisenphosphidreichen, organischen, filmbildenden Zusammensetzung beschichtet ist.

32. Beschichteter Gegenstand nach einem der Ansprüche 30 oder 31, bei dem wenigstens ein Teil der Oberfläche des Substrats mit einer nichtisolierenden Schicht aus einer phosphatisierten Epoxyzusammensetzung beschichtet ist.

33. Beschichteter Gegenstand nach einem der Ansprüche 30 oder 31, bei dem wenigstens ein Teil einer Oberfläche des Substrats zusätzlich mit einer Zinkphosphat-Vorbehandlungslösung vorbehandelt ist.

34. Beschichteter Gegenstand nach Anspruch 1, bei dem eine oder mehrere zusätzliche filmbildende Schichten auf einer freiliegenden Oberfläche der Schicht, die die elektrophoretisch abgeschiedene, filmbildende Zusammensetzung enthält, aufgebracht ist.

35. Beschichteter Gegenstand nach Anspruch 1, bei dem die elektrophoretisch abgeschiedene, filmbildende Zusammensetzung wenigstens 0,5 meq Polyharnstoffverknüpfungen pro Gramm gehärteten Film enthält.

36. Beschichteter Gegenstand nach Anspruch 35, bei dem die gehärtete, elektrophoretisch abgeschiedene Beschichtungszusammensetzung wenigstens 0,6 meq Polyharnstoffverknüpfungen pro Gramm gehärteten Film enthält.

37. Beschichteter Gegenstand nach Anspruch 35, bei dem die gehärtete, elektrophoretisch abgeschiedene Beschichtungszusammensetzung wenigstens 1,0 meq Polyharnstoffverknüpfungen pro Gramm gehärteten Film enthält.

38. Verfahren zur elektrophoretischen Beschichtung eines korrosionsbeständigen, elektrisch leitfähigen Substrats, das frei von einer elektrophoretisch abgeschiedenen Beschichtung ist, umfassend den Schritt des elektrophoretischen Abscheidens einer Beschichtungszusammensetzung auf einer Oberfläche des elektrisch leitfähigen Substrats, wobei die Beschichtungszusammensetzung ein härtbares Elastomerpolymer enthält.

39. Verfahren nach Anspruch 38, bei dem das härtbare, elastomere Polymer ein Polyurethan oder ein Polyharnstoff ist, der das Reaktionsprodukt eines Polyisocyanats und eines aktiven Wasserstoff enthaltenden elastomeren Polyesters oder Polyethers ist.

40. Verfahren nach Anspruch 39, bei dem der aktiven Wasserstoff enthaltende Polyester oder Polyether ausgewählt ist aus der Gruppe bestehend aus Polyoxyalkylenpolyolen, Polyoxyalkylenpolyaminen und Mischungen davon.

41. Verfahren nach Anspruch 39, bei dem das aktiven Wasserstoff enthaltende Polyester- oder Polyetherpolymer ausgewählt ist aus der Gruppe bestehend aus Polyoxytetramethylendiol oder -diamin, einem Polyoxypropylendiol oder -diamin, einem Polyoxyethylendiol oder -diamin und Mischungen davon.

42. Verfahren nach Anspruch 39, bei dem der aktiven Wasserstoff enthaltende Polyester oder Polyether ausgewählt ist aus der Gruppe bestehend aus Polyoxypropylendiaminen, Polyoxyethylenepropylendiaminen und Polyoxytetramethylendiaminen.

43. Verfahren nach Anspruch 40, bei dem der aktiven Wasserstoff enthaltende Polyester oder Polyether eine Glasübergangstemperatur von 0°C oder weniger und ein zahlenmittleres Molekulargewicht von 400 bis 4000 hat.

44. Verfahren nach Anspruch 38, bei dem die elektrophoretisch abgeschiedene Zusammensetzung, wenn sie gehärtet ist, wenigstens 0,5 meq Polyharnstoffverknüpfungen pro Gramm gehärteten Film enthält.

Revendications

1. Article revêtu, comprenant :

a) un substrat électriquement conducteur résistant à la corrosion qui est exempt d'un revêtement déposé électrolytiquement; et

b) une composition filmogène déposée électriquement appliquée sur au moins une partie d'une surface du substrat électriquement conducteur résistant à la corrosion, la composition filmogène comprenant un polymère élastomère électrodéposable durcissable, ledit polymère comprenant le produit de réaction d'un polyisocyanate, et d'un polymère contenant des hydrogènes actifs choisi parmi une polyéther polyamine, et/ou un mélange d'une polyéther polyamine, et d'un polyester polyol et/ou d'un polyéther polyol.

2. Article revêtu suivant la revendication 1, dans lequel la polyéther polyamine comprend une polyoxyalkylène polyamine ou un mélange d'une polyoxyalkylène polyamine et d'un polyoxyalkylène polyol.

3. Article revêtu suivant la revendication 1, dans lequel le polymère élastomère est essentiellement aliphatique.

4. Article revêtu suivant la revendication 1, dans lequel le polyisocyanate est un polyisocyanate aliphatique ou cycloaliphatique.

5. Article revêtu suivant la revendication 1, dans lequel le polyisocyanate est choisi dans le groupe comprenant l'isophorone diisocyanate, le 1,6-hexaméthylène diisocyanate, le 4,4'-diisocyanatodicyclohexyl méthane et leurs isocyanurates.

6. Article revêtu suivant la revendication 1, dans lequel la polyéther polyamine est choisie dans le groupe comprenant une polyoxytétraméthylène diamine, une polyoxypropylène polyamine, une polyéthoxyéthylène polyamine et leurs mélanges.

7. Article revêtu suivant la revendication 1, dans lequel la polyéther polyamine est (A) une polyoxytétraméthylène diamine.

8. Article revêtu suivant la revendication 7, dans lequel la polyéther polyamine comprend de plus (B) une polyoxypropylène polyamine.

9. Article revêtu suivant la revendication 8, dans lequel le rapport en poids de (A) à (B) va de 0,5 à 10/1.

10. Article revêtu suivant la revendication 1, dans lequel la polyéther polyamine comprend un mélange (i) d'une polyoxytétraméthylène diamine et (ii) d'au moins une parmi une polyoxypropylène diamine et une polyoxyéthylène diamine, dans lequel le rapport en poids de (i) à (ii) va de 0,5 à 10/1.

11. Article revêtu suivant la revendication 1, dans lequel la polyéther polyamine est choisie dans le groupe comprenant les polyoxypropylène diamines, les polyoxyéthylène-propylène diamines et les polyoxytétraméthylène diamines.

12. Article revêtu suivant la revendication 1, dans lequel la polyéther polyamine a une température de transition vitreuse de 0°C ou moins et un poids moléculaire moyen numérique allant de 400 à 4000.

13. Article revêtu suivant la revendication 1, dans lequel la polyéther polyamine est présente dans le polymère élastomère en une quantité d'au moins 30% en poids des réactifs utilisés pour fabriquer le polymère élastomère.

14. Article revêtu suivant la revendication 1, dans lequel le polymère élastomère durcissable comprend le produit de réaction i) d'un polyisocyanate, ii) d'une polyéther polyamine ayant un poids moléculaire moyen numérique supérieur à 400 et iii) d'un composé contenant des hydrogènes actifs ayant un poids moléculaire moyen numérique en dessous de 400.

15. Article revêtu suivant la revendication 1, dans lequel le polymère élastomère contient des groupes contenant des hydrogènes actifs et la composition filmogène déposée électrolytiquement comprend un agent de durcissement comportant des groupes qui sont réactifs avec les hydrogènes actifs.

16. Article revêtu suivant la revendication 15, dans lequel l'agent de durcissement est choisi dans le groupe comprenant un aminoplaste et un polyisocyanate coiffé.

17. Article revêtu suivant la revendication 15, dans lequel l'agent de durcissement est un polyisocyanate coiffé qui est coiffé d'un agent de coiffage choisi parmi le caprolactame et la dibutylamine.

18. Article revêtu suivant la revendication 15, dans lequel l'agent de durcissement est un polyisocyanate coiffé qui fait partie intégrante de la colonne vertébrale de polymère élastomère.

19. Article revêtu suivant la revendication 1, dans lequel le polymère élastomère contient des groupes contenant des hydrogènes actifs et des groupes de sel ioniques ou des groupes qui peuvent être convertis en des groupes de sel ioniques.

20. Article revêtu suivant la revendication 19, dans lequel les groupes de sel ioniques ou les groupes qui peuvent être convertis en un groupe de sel ionique sont choisis dans le groupe comprenant les groupes carboxyle et les groupes amino.

21. Article revêtu suivant la revendication 1, dans lequel la composition filmogène comprend de plus un pigment opacifiant.

22. Article revêtu suivant la revendication 21, dans lequel le pigment opacifiant est choisi dans le groupe comprenant les oxydes de fer non transparents et les oxydes de fer transparents.

23. Article revêtu suivant la revendication 1, dans lequel la composition filmogène comprend de plus un photostabilisant du type amine encombrée.

24. Article revêtu suivant la revendication 1, dans lequel la composition filmogène est une composition filmogène électrodéposable cationique.

25. Article revêtu suivant la revendication 1, dans lequel l'article revêtu comprend de plus une couche non isolante d'un revêtement résistant à la corrosion positionnée entre le substrat électriquement conducteur et la composition de revêtement.

26. Article revêtu suivant la revendication 1, dans lequel au moins une partie du substrat résistant à la corrosion est de l'acier traité en surface par du zinc ou un alliage de zinc.

27. Article revêtu suivant la revendication 26, dans lequel au moins une partie d'une surface du substrat est revêtue d'une couche non isolante d'une composition filmogène organique riche en zinc ou riche en phosphure de fer.

28. Article revêtu suivant l'une ou l'autre des revendications 26 et 27, dans lequel au moins une partie d'une surface du substrat est de plus traitée par une solution de prétraitement au phosphate de zinc.

29. Article revêtu suivant l'une ou l'autre des revendication 26 et 27, dans lequel au moins une partie d'une surface du substrat est revêtue d'une couche non isolante d'un revêtement résistant à la corrosion comprenant un composé de métal du Groupe IIIB ou IVB ou des mélanges de ceux-ci.

30. Article revêtu suivant la revendication 1, dans lequel au moins une partie du substrat résistant à la corrosion est de l'aluminium ou un alliage de celui-ci.

31. Article revêtu suivant la revendication 30, dans lequel au moins une partie de la surface du substrat est revêtue d'une couche non isolante d'une composition filmogène organique riche en zinc ou riche en phosphorure de fer.

32. Article revêtu suivant l'une ou l'autre des revendications 30 et 31, dans lequel au moins une partie de la surface du substrat est revêtue d'une couche non isolante d'une composition d'époxy phosphatée.

33. Article revêtu suivant l'un ou l'autre des revendications 30 et 31, dans lequel au moins une partie d'une surface du substrat est de plus traitée par une solution de prétraitement au phosphate de zinc.

34. Article revêtu suivant la revendication 1, dans lequel une ou plusieurs couches filmogènes additionnelles sont appliquées à une surface exposée de la couche comprenant la composition filmogène déposée électrolytiquement.

35. Article revêtu suivant la revendication 1, dans lequel la composition filmogène déposée électrolytiquement durcie comprend au moins 0,5 méq de liaisons de polyurée par gramme de film durci.

36. Article revêtu suivant la revendication 35, dans lequel la composition de revêtement déposée électrolytiquement durcie comprend au moins 0,6 méq de liaisons de polyurée par gramme de film durci.

37. Article revêtu suivant la revendication 35, dans lequel la composition de revêtement déposée électrolytiquement durcie comprend au moins 1,0 méq de liaisons de polyurée par gramme de film durci.

38. Procédé de revêtement électrolytique d'un substrat électriquement conducteur résistant à la corrosion, qui est exempt d'un revêtement déposé électrolytiquement, comprenant l'étape d'électrodéposition d'une composition de revêtement sur une surface du substrat électriquement conducteur, la composition de revêtement comprenant un polymère élastomère durcissable.

39. Procédé suivant la revendication 38, dans lequel le polymère élastomère durcissable est un polyuréthanne ou une polyurée qui comprend le produit de réaction d'un polyisocyanate et d'un polyester ou polyéther élastomère comprenant des hydrogènes actifs.

40. Procédé suivant la revendication 39, dans lequel le polyester ou polyéther contenant des hydrogènes actifs est choisi dans le groupe comprenant les polyoxyalkylène polyols, les polyoxyalkylène polyamines et leurs mélanges.

41. Procédé suivant la revendication 39, dans lequel le polymère de polyester ou polyéther contenant des hydrogènes actifs est choisi dans le groupe comprenant un polyoxytétraméthylène diol ou diamine, un polyoxypropylène diol ou diamine, un polyoxyéthylène diol ou diamine et leurs mélanges.

42. Procédé suivant la revendication 39, dans lequel le polyester ou polyéther contenant des hydrogènes actifs est choisi dans le groupe comprenant les polyoxypropylène diamines, les polyoxyéthylène-propylène diamines et les polyoxytétraméthylène diamines.

43. Procédé suivant la revendication 40, dans lequel le polyester ou polyéther contenant des hydrogènes actifs a une température de transition vitreuse de 0°C ou moins et un poids moléculaire moyen numérique de 400-4000.

44. Procédé suivant la revendication 38, dans lequel la composition de revêtement déposée électrolytiquement, lorsque durcie, comprend au moins 0,5 méq de liaisons de polyurée par gramme de film durci.